Ethylene (or IUPAC name ethene) is the chemical compound with the formula C2H4. It is the simplest alkene. Because it contains a double bond, ethylene is called an unsaturated hydrocarbon or an olefin. It is extremely important in industry and even has a role in biology as a hormone.[1] Ethylene is the most produced organic compound in the world; global production of ethylene exceeded 75 million metric tons per year in 2005.[2]

Structure

This hydrocarbon has four hydrogenatoms bound to a pair of carbon atoms that are connected by a double bond. All six atoms that comprise ethylene are coplanar. The H-C-H angle is 117°, close to the 120°For ideal sp² hybridized carbon. The molecule is also relatively rigid: rotation about the C-C bond is a high energy process that requires breaking the π-bond, while retaining the σ-bond between the carbon atoms.

The double bond is a region of high electron density, and most reactions occur at this double bond position.

History

From 1795 on, ethylene was referred to as the olefiant gas (oil-making gas), because it combined with chlorine to produce the oil of the Dutch chemists (1,2-dichloroethane), first synthesized in 1795 by a collaboration of four Dutch chemists.

In the mid-19th century, the suffix -ene (an Ancient Greek root added to the end of female names meaning "daughter of") was widely used to refer to a molecule or part thereof that contained one fewer hydrogen atoms than the molecule being modified. Thus, ethylene (C2H4) was the "daughter of ethyl" (C2H5). The name ethylene was used in this sense as early as 1852.

In 1866, the German chemist August Wilhelm von Hofmann proposed a system of hydrocarbon nomenclature in which the suffixes -ane, -ene, -ine, -one, and -une were used to denote the hydrocarbons with 0, 2, 4, 6, and 8 fewer hydrogens than their parent alkane[1]. In this system, ethylene became ethene. Hofmann's system eventually became the basis for the Geneva nomenclature approved by the International Congress of Chemists in 1892, which remains at the core of the IUPAC nomenclature. However, by that time, the name ethylene was deeply entrenched, and it remains in wide use today, especially in the chemical industry.

The 1979 IUPAC nomenclature rules make an exception for retaining the non-systematic name ethylene[3], however, this decision was reversed in the 1993 rules[4].

Production

Ethylene is produced in the petrochemical industry by steam "cracking". In this process, gaseous or light liquid hydrocarbons are briefly heated to 750–950 °C, inducing numerous free radicalreactions. This process converts large hydrocarbons into smaller ones and introduces unsaturation. Ethylene is separated from the resulting complex mixture by repeated compression and distillation. In a related process used in oil refineries, high molecular weight hydrocarbons are cracked over Zeolite catalysts. Heavier feedstocks, such as naphtha and gas oils require at least two "quench towers" downstream of the cracking furnaces to recirculate pyrolysis-derived gasoline and process water. When cracking a mixture of ethane and propane, only one water quench tower is required.[5]

The areas of an ethylene plant are:
1) steam cracking furnaces;
2) primary and secondary heat recovery with quench;
3) a dilution steam recycle system between the furnaces and the quench system;
4) primary compression of the cracked gas (3 stages of compression);
5) hydrogen sulfide and carbon dioxide removal (acid gas removal);
6) secondary compression (1 or 2 stages);
7) drying of the cracked gas;
8) cryogenic treatment;
9) all of the cold cracked gas stream goes to the demethanizer tower. The overhead stream from the demethanizer tower consists of all the hydrogen and methane that was in the cracked gas stream. Different methods of cryogenically treating this overhead stream results in the separation of the hydrogen and the methane. This usually involves liquid methane at a temperature around -250 degrees F. Complete recovery of all the methane is critical to the economical operation of an ethylene plant.
10) the bottom stream from the demethanizer tower goes to the deethanizer tower. The overhead stream from the deethanizer tower consists of all the C2,'s that were in the cracked gas stream. The C2's then go to a C2 splitter. The product ethylene is taken from the overhead of the tower and the ethane coming from the bottom of the splitter is recycled to the furnaces to be cracked again;
11) the bottom stream from the deethanizer tower goes to the depropanizer tower. The overhead stream from the depropanizer tower consists of all the C3's that were in the cracked gas stream. Prior to sending the C3's to the C3 splitter this stream is hydrogenated in order to react out the methylacetylene and propadiene. Then this stream is sent to the C3 splitter. The overhead stream from the C3 splitter is product propylene and the bottom stream from the C3 splitter is propane which can be sent back to the furnaces for cracking or used as fuel.
12) The bottom stream from the depropanizer tower is fed to the debutanizer tower. The overhead stream from the debutanizer is all of the C4's that was in the cracked gas stream. The bottom stream from the debutanizer consists of everything in the cracked gas stream that is C5 or heavier. This could be called a light pyrolysis gasoline.[5]

Since the production of ethylene is energy intensive, much effort has been dedicated recovering heat from the gas leaving the furnaces. Most of the energy recovered from the cracked gas is used to make high pressure (1200 psig) steam. This steam is in turn used to drive the turbines for compressing cracked gas, the propylene refrigeration compressor, and the ethylene refrigeration compressor. An ethylene plant, once running, does not need to import any steam to drive its steam turbines. A typical world scale ethylene plant (about 1.5 billion pounds of ethylene per year) uses a 45,000 horsepower cracked gas compressor, a 30,000 horsepower propylene compressor, and a 15,000 horsepower ethylene compressor.

When starting an ethylene plant it is important to start the cooling systems in the proper order. The cooling systems consist of Cooling Tower Water (CTW); propylene refrigeration with four or five different levels or stages. Each level corresponds to a particular pressure and temperature; and three or four stages of ethylene regfrigeration. The CTW must be started first because the propylene system needs it to condense propylene and the ethylene refrigeration systems needs it to desuperheat high pressure ethylene. The propylene system must start next because the ethylene system needs high pressure propylene for desuperheating the high pressure ethylene stage and the low pressure propylene stage for condensing the high pressure ethylene. While the ethylene plant is running, the plant can continue to run for a time if the ethylene refrigeration compressor shuts down. However, if the propylene compressor shuts down the whole plant must be shut down immediately.[5]

Peculiarity of spectrum

Although ethylene is a relatively simple molecule, its spectrum[6] is considered to be one of the most difficult to explain adequately from both a theoretical and practical perspective. For this reason, it is often used as a test case in computational chemistry. Of particular note is the difficulty in characterizing the ultraviolet absorption of the molecule. Interest in the subtleties and details of the ethylene spectrum can be dated back to at least the 1950s.

Additions to double bond

Like most alkenes, ethylene reacts with halogens to produce halogenated hydrocarbons1,2-C2H4X2. It can also react with water to produce ethanol, but the rate at which this happens is very slow unless a suitable catalyst, such as phosphoric or sulfuric acid, is used. Under high pressure, and, in the presence of a catalytic metal (platinum, rhodium, nickel), hydrogen will react with ethylene to form ethane.

1. It has a double bond, one called the π-bond(pi) and one called the σ-bond (sigma). Where π-bond is weak and σ-bond is strong. The presence of the π-bond makes it a high energy molecule. Thus bromine water decolourises readily when it is added to ethylene.

2. High electron density at the double bond makes it react readily. It is broken in an addition reaction to produce many useful products.

Oxidation

Ethylene undergoes oxidation by palladium to give acetaldehyde. This conversion was at one time a major industrial process.[7] The process proceeds via the initial complexation of ethylene to a Pd(II) center.

History of ethylene in plant biology

Ethylene has been used in practice since the ancient Egyptians, who would gas figs in order to stimulate ripening. The ancient Chinese would burn incense in closed rooms to enhance the ripening of pears. In 1864, it was discovered that gas leaks from street lights led to stunting of growth, twisting of plants, and abnormal thickening of stems (Arteca, 1996; Salisbury and Ross, 1992). In 1901, a Russian scientist named Dimitry Neljubow showed that the active component was ethylene (Neljubow, 1901). Doubt discovered that ethylene stimulated abscission in 1917 (Doubt, 1917). It wasn't until 1934 that Gane reported that plants synthesize ethylene (Gane, 1934). In 1935, Crocker proposed that ethylene was the plant hormone responsible for fruit ripening as well as inhibition of vegetative tissues (Crocker, 1935).

Ethylene biosynthesis in plants

It has been shown that ethylene is produced from essentially all parts of higher plants, including leaves, stems, roots, flowers, fruits, tubers, and seedlings.

"Ethylene production is regulated by a variety of developmental and environmental factors. During the life of the plant, ethylene production is induced during certain stages of growth such as germination, ripening of fruits, abscission of leaves, and senescence of flowers. Ethylene production can also be induced by a variety of external aspects such as mechanical wounding, environmental stresses, and certain chemicals including auxin and other regulators"[12]

The biosynsthesis of the hormone starts with conversion of the amino acid methionine to S-adenosyl-L-methionine (SAM, also called Adomet) by the enzyme Met Adenosyltransferase. SAM is then converted to 1-aminocyclopropane-1-carboxylic-acid (ACC) by the enzyme ACC synthase (ACS); the activity of ACS is the rate-limiting step in ethylene production, therefore regulation of this enzyme is key for the ethylene biosynthesis. The final step requires oxygen and involves the action of the enzyme ACC-oxidase (ACO), formerly known as the Ethylene Forming Enzyme (EFE).

The pathway can be represented as follows:

Methionine --> SAM --> ACC --> Ethylene

Ethylene biosynthesis can be induced by endogenous or exogenous ethylene. ACC synthesis increases with high levels of auxins, specially Indole Acetic Acid (IAA), and cytokinins. ACC synthase is inhibited by abscisic acid.

Ethylene perception in plants

Ethylene is perceived by a transmembrane protein dimer complex. The first gene encoding an ethylene receptor was first cloned from Arabidopsis thaliana by Caren Chang, Elliot Meyerowitz and colleagues at the California Institute of Technology[13] and then in tomato by Jack Wilkinson, Harry Klee and colleagues at the Monsanto Company[14]. Ethylene receptors are encoded by multiple genes in the Arabidopsis and tomato genomes. The gene family is comprised of five receptors in Arabidopsis and six in tomato, all of which have been shown to bind ethylene. DNA sequences for ethylene receptors have also been identified in many other plant species and have even been identified in Cyanobacteria[15]

Environmental and biological triggers of ethylene

Environmental cues can induce the biosynthesis of the plant hormone. Flooding, drought, chilling, wounding, and pathogen attack can induce ethylene formation in the plant.

In flooding, root suffers from lack of oxygen, or anoxia, which leads to the synthesis of 1-Aminocyclopropane-1-carboxylic acid (ACC). ACC is transported upwards in the plant and then oxidized in leaves. The product, the ethylene causes epinasty of the leaves.

One speculation recently put forth for epinasty [2] is the downard pointing leaves may act as pump handles in the wind. The ethylene may or may not additionally induce the growth of a valve in the xylem, but the idea would be that the plant would harness the power of the wind to pump out more water from the roots of the plants than would normally happen with transpiration.

Physiological responses of plants

Like the other plant hormones, ethylene is considered to have pleiotropic effects. This essentially means that it is thought that at least some of the effects of the hormone are unrelated. What is actually caused by the gas may depend on the tissue affected as well as environmental conditions. In the evolution of plants, ethylene would simply be a message that was coopted for unrelated uses by plants during different periods of the evolutionary development.

List of Plant Responses to Ethylene

Seedling triple response, thickening and shortening of hypocotyl with pronounced apical hook. This thought to be a seedlings reaction to an obstacle in the soil such a stone, allowing it to push past the obstruction.

In pollination, when the pollen reaches the stigma, the precursor of the ethylene, ACC, is secreted to the petal, the ACC releases ethylene with ACC oxidase.

Induces a climacteric rise in respiration in some fruit which causes a release of additional ethylene. This can be the one bad apple in a barrel spoiling the rest phenomenon.

Affects neighboring individuals

Disease/wounding resistance

Triple response when applied to seedlings – stem elongation slows, the stem thickens, and curvature causes the stem to start growing horizontally. This strategy is thought to allow a seedling grow around an obstacle

Commercial Issues

Ethylene shortens the shelf life of many fruits by hastening fruit ripening and floral senescence. Tomatoes, bananas, and apples will ripen faster in the presence of ethylene. Bananas placed next to other fruits will produce enough ethylene to cause accelerated fruit ripening.
Ethylene will shorten the shelf life of cut flowers and potted plants by accelerating floral senescence and floral abscission. Flowers and plants which are subjected to stress during shipping, handling, or storage produce ethylene causing a significant reduction in floral display. Flowers affected by ethylene include carnation, geranium, petunia, rose, and many others[16].

Ethylene can cause significant economic losses for florists, markets, suppliers, and growers. Researchers have come up with several ways to inhibit ethylene, including inhibiting ethylene synthesis and inhibiting ethylene perception. Inhibiting ethylene synthesis is less effective for reducing post-harvest losses since ethylene from other sources can still have an effect. By inhibiting ethylene perception, fruits, plants and flowers don't respond to ethylene produced endogenously or from exogenous sources. Inhibitors of ethylene perception include compounds that have a similar shape to ethylene, but do not elicit the ethylene response. An example of an ethylene perception inhibitor is 1-methylcyclopropene (1-MCP).

Commercial growers of bromeliads, including pineapple plants, use ethylene to induce flowering. Plants can be induced to flower either be treated with the gas in a chamber or by placing a banana peel next to the plant in an enclosed area.

Symptoms

Ethylene has a pleasant sweet faint odor, and has a slightly sweet taste, and as it enhances fruit ripening, assists in the development of odour-active aroma volatiles (especially esters), which are responsible for the specific smell of each kind of flower or fruit.

In mild doses, ethylene produces states of euphoria, associated with stimulus to the pleasure centres of the human brain. It has been hypothesised that human liking for the odours of flowers is due in part to a mild action of ethylene associated with the plant.[citation needed]

Exposure at 37.5% for 15 minutes may result in marked memory disturbances. Humans exposed to as much as 50% ethylene in air, whereby the oxygen availability is decreased to 10%, experience a complete loss of consciousness and may subsequently die due to hypoxia.

General alertness level is somewhat reduced to anything but central concerns

Symptoms may begin in those patients with pre-existing significant cardiac, pulmonary, or hematologic diseases.

Euphoria

High concentration in air

Percent of O2 saturation at 64 to 82%

Compensatory mechanisms increasingly become inadequate

Air hunger, gasping for breath

Fatigue, lassitude, inability to maintain balance

Tunnel vision, out-of-body experiences

Dizziness

Mild to persistent headache

Belligerence, certainty of truth

Extreme euphoria, belief in capacities of the self enhanced

Visual acuity is reduced, dreamlike seeing of visions

Numbness and tingling of extremities

Hyperventilation

Distortions of judgment, abnormal or illogical inferences drawn

Memory loss after event

Increased cyanosis

Decreased ability for escape from toxic environment

Very high concentration in air

Percent of O2 saturation at 60 to 70% or less

Further deterioration in judgment and coordination may occur in 3 to 5 minutes or less

Severe oxygen deprivation

Loss of consciousness results when the air contains about 11% of oxygen.

Death occurs quickly when the oxygen content falls to 8% or less.

Very high concentrations in oxygen

Prolonged inhalation of about 85% in oxygen is slightly toxic, resulting in a slow fall in blood pressure.

At about 94% in oxygen, ethylene is acutely fatal.

Medical and historical use

Ethylene has long been in use as an inhalatory anaesthetic. When used as a surgical anaesthetic, it is always administered with oxygen with an increased risk of fire. In such cases, however, it acts as a simple, rapid anaesthetic having a quick recovery.

Many geologists and scholars believe that the famous Greek Oracle at Delphi (the Pythia) went into her trance-like state as an affect of ethylene rising from ground faults.[17]

Safety

There is no evidence to indicate that prolonged exposure to low concentrations of ethylene can result in chronic effects. Prolonged exposure to high concentrations may cause permanent effects because of oxygen deprivation. Prolonged inhalation of about 85% in oxygen (a relatively high concentration) is also slightly toxic, resulting in a slow fall in blood pressure. At about 94% in oxygen, ethylene is acutely fatal.

It shows little or no carcinogenic or mutagenic properties. Although there may be moderate hyperglycemia, post operative nausea - while higher than nitrous oxide - is less than in the use of cyclopropane. During the induction and early phases, blood pressure may rise a little, but this effect may be due to patient anxiety, as blood pressure quickly returns to normal. Cardiac arrythmias are infrequent and cardio-vascular effects are benign.